Laundry detergent composition containing two graft copolymer

ABSTRACT

A laundry detergent composition containing two graft copolymers.

FIELD OF THE INVENTION

The present invention relates to a laundry detergent compositioncontaining two graft copolymers.

BACKGROUND OF THE INVENTION

As detergent products are evolving, consumer needs in the term ofcleaning have been well met. However, there are still some other unmetconsumer needs in the field of laundry. Particularly, the unmet needsinclude additional benefits for fabrics after washing, e.g. a delightfulscent, brightening, degerming, anti-malodor, softening, and insectrepelling. Especially, perfumes have typically been used to helpcounteract malodour and also to make clothing smell “fresh”. In order todeliver such freshness, it is known that perfume can be added intolaundry products.

However, the freshness is often unsatisfactory due to insufficientdeposition of such perfume onto fabrics after washing. Accordingly, itmay be desirable to have technologies to improve the deposition ofperfume onto fabrics.

SUMMARY OF THE INVENTION

It is a surprising and unexpected discovery of the present inventionthat the combination of two graft copolymers in a detergent formulationcan deliver a synergistic effect on the deposition of perfume, resultingin improved freshness.

Correspondingly, the present invention in one aspect relates to alaundry detergent composition, comprising:

-   -   1) a first graft copolymer comprising:    -   a) polyalkylene oxide component as a graft base which has a        number average molecular weight of from 1000 to 20,000 Daltons        and is based on ethylene oxide, propylene oxide, butylene oxide        or mixtures thereof;    -   b) N-vinylpyrrolidone; and    -   c) vinyl ester derived from a saturated monocarboxylic acid        containing from 1 to 6 carbon atoms and/or a methyl or ethyl        ester of acrylic or methacrylic acid;    -   wherein the weight ratio of (a):(b) is from 1:0.1 to 1:2, and    -   wherein the amount, by weight, of (a) is greater than the amount        of (c);    -   2) a second graft copolymer comprising:    -   i) polyalkylene oxide component as a graft base which preferably        has a number average molecular weight of from 1000 to 20,000        Daltons and is based on ethylene oxide, propylene oxide,        butylene oxide or mixtures thereof; and    -   ii) vinyl ester component as side chains which is preferably        derived from a saturated monocarboxylic acid containing from 1        to 6 carbon atoms and/or a methyl or ethyl ester of acrylic or        methacrylic acid;    -   and    -   3) a perfume.

In one embodiment according to the present application, the weight ratioof the first graft copolymer to the second graft copolymer is from 20:1to 1:20, preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5,most preferably from 3:1 to 1:3.

In one embodiment according to the present application, the total amountof the first graft copolymer and the second graft copolymer is from0.05% to 3%, preferably from 0.05% to 2.5%, more preferably from 0.1% to2%, yet more preferably from 0.15% to 1.5%, yet more preferably from0.2% to 1%, most preferably 0.2% to 0.7%, e.g. 1%, 0.9%, 0.8%, 0.7%,0.6%, 0.5%, 0.4%, 0.2% or any ranges therebetween, by weight of thecomposition.

In one embodiment according to the present application, in the firstgraft copolymer:

-   -   a) the polyalkylene oxide comprises and preferably consists of        ethylene oxide units or ethylene oxide units and propylene oxide        units, and    -   c) the vinyl ester comprises and preferably consists of vinyl        acetate.

In one embodiment according to the present application, in the firstgraft copolymer, the polyalkylene oxide has a number average molecularweight of from 2000 to 15,000 Daltons.

In one embodiment according to the present application, in the firstgraft polymer, the weight ratio of (a):(c) is from 1.0:0.1 to 1.0:0.99,preferably from 1.0:0.3 to 1.0:0.9.

In one embodiment according to the present application, in the firstgraft polymer, from 1.0 mol % to 60 mol %, preferably from 20 mol % to60 mol %, more preferably from 30 mol % to of the grafted-on monomers ofcomponent (c) are hydrolysed.

In one embodiment according to the present application, the first graftpolymer has a weight average molecular weight of from 4,000 Da to100,000 Da, preferably 5,000 Da to 100,000 Da, more preferably from5,000 Da to 50,000 Da, most preferably from 8,000 Da to 20,000 Da.

Preferably, the second graft copolymer has an average of greater than 0to less than or equal to 1 graft site per 50 alkylene oxide units,and/or the second graft copolymer has from 20% to 70%, preferably from25% to 60%, by weight of said polymer of the polyalkylene oxidecomponent and from 30% to 80%, preferably from 40% to 75%, by weight ofsaid polymer of the vinyl ester component, and/or the second graftcopolymer has a mean molar mass Mw of from 3,000 to 60,000, preferablyfrom 6,000 to 45,000; and/or the second graft copolymer has apolydispersity of less than or equal to 3; and/or the second graftcopolymer comprises less than or equal to 10% by weight of the polyvinylester in ungrafted form; and/or the second graft copolymer comprisesside chains consisting of the vinyl ester component.

In one embodiment according to the present application, the compositioncomprises:

-   -   from about 0.01% to about 5%, preferably from about 0.05% to        about 2%, more preferably from about 0.1% to about 1%, and most        preferably from about 0.1% to about 0.5%, by weight of the        composition, of the first graft copolymer, and/or    -   from about 0.01% to about 5%, preferably from about 0.05% to        about 2%, more preferably from about 0.1% to about 1%, and most        preferably from about 0.1% to about 0.5%, by weight of the        composition, of the second graft copolymer, and/or    -   from about 0.001% to about 5%, preferably from about 0.005% to        about 3%, more preferably from about 0.008% to about 2%, and        most preferably from about 0.01% to about 1%, by weight of the        composition, of the perfume.

In one embodiment according to the present application, the compositionfurther comprises from 0.1% to 70%, preferably from 1% to 50%, morepreferably from 5% to 40%, most preferably from 10% to 35%, by weight ofthe composition, of a surfactant.

In one embodiment according to the present application, the surfactantcomprises C₆-C₂₀ linear alkylbenzene sulfonate (LAS), C₆-C₂₀ alkylalkoxy sulfates (AAS), C₆-C₂₀ alkoxylated alcohol, or any mixturesthereof.

In one embodiment according to the present application, the compositionmay further comprise a treatment adjunct which may be preferablyselected from the group consisting of a surfactant system, fatty acidsand/or salts thereof, soil release polymers, hueing agents, builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymestabilizers, anti-oxidants, catalytic materials, bleach catalysts,bleach activators, polymeric dispersing agents, soilremoval/anti-redeposition agents, polymeric grease cleaning agents,amphiphilic copolymers, suds suppressors, dyes, hueing agents, structureelasticizing agents, carriers, fillers, hydrotropes, solvents,anti-microbial agents and/or preservatives, neutralizers and/or pHadjusting agents, processing aids, rheology modifiers and/orstructurants, opacifiers, pearlescent agents, pigments, anti-corrosionand/or anti-tarnishing agents, and mixtures thereof.

In one embodiment according to the present application, said compositionis in the form of a liquid composition, a granular composition, asingle-compartment pouch, a multi-compartment pouch, a sheet, a pastilleor bead, a fibrous article, a tablet, a bar, flake, or a mixturethereof. In one embodiment, the composition is added to a washingmachine dispenser, or directly to the drum, manually or automatically inan auto-dosing machine.

In another aspect, the present application is related to the use of alaundry detergent composition according to the present application forimproving the deposition of the perfume onto fabrics, especiallysynthetic fabrics.

In another aspect, the present application is related to a method oftreating textile, the method comprising the steps of: (i) treating atextile with a laundry detergent composition according to the presentapplication; and (ii) treating the textile with a fabric enhancercomposition comprising a perfume. Particularly, the fabric enhancercomposition is a solid fabric enhancer composition and Step (ii) occurswhen the textile is washed. Alternatively, the fabric enhancercomposition is a liquid fabric enhancer composition and Step (ii) occurswhen the textile is rinsed.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the articles including “a” and “an” when used in aclaim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “comprise”, “comprises”, “comprising”,“include”, “includes”, “including”, “contain”, “contains”, and“containing” are meant to be non-limiting, i.e., other steps and otheringredients which do not affect the end of result can be added. Theabove terms encompass the terms “consisting of” and “consistingessentially of”.

As used herein, when a composition is “substantially free” of a specificingredient, it is meant that the composition comprises less than a traceamount, alternatively less than 0.1%, alternatively less than 0.01%,alternatively less than 0.001%, by weight of the composition, of thespecific ingredient.

As used herein, the term “laundry detergent composition” means acomposition for cleaning soiled materials, including fabrics. Suchcompositions may be used as a pre-laundering treatment, apost-laundering treatment, or may be added during the rinse or washcycle of the laundering operation, may be added manually by the consumeror automatically by an automatic dispensing machine. The laundrydetergent composition compositions may have a form selected from liquid,powder, unit dose such as single-compartment or multi-compartment unitdose, pouch, tablet, gel, paste, bar, or flake. Preferably, the laundrydetergent composition is a liquid or a unit dose composition. The termof “liquid laundry detergent composition” herein refers to compositionsthat are in a form selected from the group consisting of pourableliquid, gel, cream, and combinations thereof. The liquid laundrydetergent composition may be either aqueous or non-aqueous, and may beanisotropic, isotropic, or combinations thereof. The term of “unit doselaundry detergent composition” herein refers to a water-soluble pouchcontaining a certain volume of liquid wrapped with a water-soluble film.

As used herein, the term “alkyl” means a hydrocarbyl moiety which isbranched or unbranched, substituted or unsubstituted. Included in theterm “alkyl” is the alkyl portion of acyl groups.

As used herein, the term “washing solution” refers to the typical amountof aqueous solution used for one cycle of laundry washing, from 1 L to65 L, preferably from 1 L to 50 L, alternatively from 1 L to 20 L forhand washing and from 10 L to 50 L for machine washing.

As used herein, the term “soiled fabric” is used non-specifically andmay refer to any type of natural or artificial fibers, includingnatural, artificial, and synthetic fibers, such as, but not limited to,cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, aswell as various blends and combinations.

Composition

The compositions of the present disclosure may be selected from thegroup of light duty liquid detergents compositions, heavy duty liquiddetergent compositions, detergent gels commonly used for laundry,bleaching compositions, laundry additives, fabric enhancer compositions,and mixtures thereof.

The composition may be in any suitable form. The composition may be inthe form of a liquid composition, a granular composition, asingle-compartment pouch, a multi-compartment pouch, a sheet, a pastilleor bead, a fibrous article, a tablet, a bar, flake, or a mixturethereof. The composition can be selected from a liquid, solid, orcombination thereof.

The composition can be an aqueous liquid laundry detergent composition.For such aqueous liquid laundry detergent compositions, the watercontent can be present at a level of from 5.0% to %, preferably from 25%to 90%, more preferably from 50% to 85% by weight of the liquiddetergent composition.

The pH range of the detergent composition is from 6.0 to 8.9, preferablyfrom pH 7 to 8.8.

The detergent composition can also be encapsulated in a water-solublefilm, to form a unit dose article. Such unit dose articles comprise adetergent composition of the present invention, wherein the detergentcomposition comprises less than 20%, preferably less than 15%, morepreferably less than 10% by weight of water, and the detergentcomposition is enclosed in a water-soluble or dispersible film. Suchunit-dose articles can be formed using any means known in the art.Suitable unit-dose articles can comprise one compartment, wherein thecompartment comprises the liquid laundry detergent composition.Alternatively, the unit-dose articles can be multi-compartment unit-dosearticles, wherein at least one compartment comprises the liquid laundrydetergent composition.

First Graft Copolymers

The detergent composition may comprise a first graft copolymer. Thefirst graft copolymer can be present at a level of from about 0.01% toabout 15%, preferably from about 0.05% to about 10%, more preferablyfrom about 0.1% to about 5%, and most preferably from about 0.2% toabout 3%, e.g. 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%,1%, 2%, or 3%, by weight of the composition.

The first graft copolymer comprises: (a) polyalkylene oxide which has anumber average molecular weight of from 1000 to 20,000 Daltons and isbased on ethylene oxide, propylene oxide, or butylene oxide, (b)N-vinylpyrrolidone, and (c) vinyl ester derived from a saturatedmonocarboxylic acid containing from 1 to 6 carbon atoms, wherein theweight ratio of (a):(b) is from 1:0.1 to 1:2, preferably from 1:0.1 to1:1, more preferably from 1:0.3 to 1:1, and wherein the amount, byweight, of (a) is greater than the amount of (c).

The weight ratio of (a):(c) is from 1.0:0.1 to 1.0:0.99, or from 1.0:0.3to 1.0:0.9. The weight ratio of (b):(c) can be from 1.0:0.1 to 1.0:5.0,or to 1.0:4.0.

The amount, by weight of the polymer, of (a) is greater than the amountof (c). The polymer may comprise at least 50% by weight, preferably atleast 60% by weight, more preferably at least 75% by weight of (a)polyalkylene oxide.

The first graft copolymer comprises and/or is obtainable by grafting (a)a polyalkylene oxide which has a number average molecular weight of from1000 to 20000 Da, or to 15000, or to 12000 Da, or to 10000 Da and isbased on ethylene oxide, propylene oxide, or butylene oxide, preferablybased on ethylene oxide, with (b) N-vinylpyrrolidone, and further with(c) a vinyl ester derived from a saturated monocarboxylic acidcontaining from 1 to 6 carbon atoms, preferably a vinyl ester that isvinyl acetate or a derivative thereof.

Suitable polyalkylene oxides may be based on homopolymers or copolymers,with homopolymers being preferred. Suitable polyalkylene oxides may bebased on homopolymers of ethylene oxide or ethylene oxide copolymershaving an ethylene oxide content of from 40 mol % to 99 mol %. Suitablecomonomers for such copolymers may include propylene oxide, n-butyleneoxide, and/or isobutylene oxide. Suitable copolymers may includecopolymers of ethylene oxide and propylene oxide, copolymers of ethyleneoxide and butylene oxide, and/or copolymers of ethylene oxide, propyleneoxide, and at least one butylene oxide. The copolymers may include anethylene oxide content of from 40 to 99 mol %, a propylene oxide contentof from 1.0 to 60 mol %, and a butylene oxide content of from 1.0 to 30mol %. The graft base may be linear (straight-chain) or branched, forexample a branched homopolymer and/or a branched copolymer.

Branched copolymers may be prepared by addition of ethylene oxide withor without propylene oxides and/or butylene oxides onto polyhydric lowmolecular weight alcohols, for example trimethylol propane, pentoses, orhexoses.

The alkylene oxide unit may be randomly distributed in the polymer or bepresent therein as blocks.

The polyalkylene oxides of component (a) may be the correspondingpolyalkylene glycols in free form, that is, with OH end groups, or theymay be capped at one or both end groups. Suitable end groups may be, forexample, C1-C25-alkyl, phenyl, and C1-C14-alkylphenyl groups. The endgroup may be a C1-alkyl (e.g., methyl) group. Suitable materials for thegraft base may include PEG 300, PEG 1000, PEG 2000, PEG 4000, PEG 6000,PEG 8000, PEG 10000, PEG 12000, and/or PEG 20000, which are polyethyleneglycols, and/or MPEG 2000, MPEG 4000, MPEG 6000, MPEG 8000 and MEG 10000which are monomethoxypolyethylene glycols that are commerciallyavailable from BASF under the tradename PLURIOL and/or block copolymersmade from ethylene oxide-propylene oxide-ethylene oxide (EO-PO-EO) orfrom propylene oxide-ethylene oxide-propylene oxide (PO-EO-PO) such asPE 6100, PE 6800 or PE 3100 commercially available from BASF under thetradename PLURONIC.

The first graft copolymer of the present disclosure may be characterizedby relatively low degree of branching (i.e., degree of grafting). In thefirst graft copolymer of the present disclosure, the average number ofgrafting sites may be less than or equal to 1.0, or less than or equalto 0.8, or less than or equal to 0.6, or less than or equal to 0.5, orless than or equal to 0.4, per 50 alkylene oxide groups, e.g., ethyleneoxide groups. The first graft copolymer may comprise, on average, basedon the reaction mixture obtained, at least 0.05, or at least 0.1, graftsite per 50 alkylene oxide groups, e.g., ethylene oxide groups. Thedegree of branching may be determined, for example, by means of ¹³C NMRspectroscopy from the integrals of the signals of the graft sites andthe —CH₂— groups of the polyalkylene oxide.

The number of grafting sites may be adjusted by manipulating thetemperature and/or the feed rate of the monomers. For example, thepolymerization may be carried out in such a way that an excess ofcomponent (a) and the formed graft copolymer is constantly present inthe reactor. For example, the quantitative molar ratio of component (a)and polymer to ungrafted monomer (and initiator, if any) is generallygreater than or equal to 10:1, or to 15:1, or to 20:1.

The polyalkylene oxides are grafted with N-vinylpyrrolidone as themonomer of component (b). Without wishing to be bound by theory, it isbelieved that the presence of the N-vinylpyrrolidone (“VP”) monomer inthe first graft copolymers according to the present disclosure provideswater-solubility and good film-forming properties compared tootherwise-similar polymers that do not contain the N-vinylpyrrolidonemonomer. The vinyl pyrrolidone repeat unit has amphiphilic characterwith a polar amide group that can form a dipole, and a non-polar portionwith the methylene groups in the backbone and the ring, making ithydrophobic.

The polyalkylene oxides are grafted with a vinyl ester as the monomer ofcomponent (c). The vinyl ester may be derived from a saturatedmonocarboxylic acid, which may contain 1 to 6 carbon atoms, or from 1 to3 carbon atoms, or from 1 to 2 carbon atoms, or 1 carbon atom. Suitablevinyl esters may be selected from the group consisting of vinyl formate,vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyliso-valerate, vinyl caproate, or mixtures thereof. Preferred monomers ofcomponent (c) include those selected from the group consisting of vinylacetate, vinyl propionate, or mixtures thereof, preferably vinylacetate.

Conventionally, molecular weights are expressed by their “K-values,”which are derived from relative viscosity measurements. The first graftcopolymer may have a K value of from 5.0 to 200, optionally from 5.0 to50, determined according to H. Fikentscher in 2% strength by weightsolution in dimethylformamide at 25 C.

The first graft copolymer of the present disclosure may be characterizedby a relatively narrow molar mass distribution. For example, the firstgraft copolymer may be characterized by a polydispersity M_(w)/M_(n) ofless than or equal to 3.0, or less than or equal to 2.5, or less than orequal to 2.3. The polydispersity of the first graft copolymer may befrom 1.5 to 2.2. The polydispersity may be determined by gel permeationchromatography using organic solvent such as hexafluoroisopropanol(HFIP) with multi-angle laser light scattering detection.

The mean molecular weight Mw of the preferred graft polymers may be from3000 to 100,000, preferably from 6000 to 45,000, and more preferablyfrom 8000 to 30,000 Da.

The first graft copolymer may be prepared by grafting the suitablepolyalkylene oxides of component (a) with the monomers of component (b)in the presence of free radical initiators and/or by the action ofhigh-energy radiation, which may include the action of high-energyelectrons. This may be done, for example, by dissolving the polyalkyleneoxide in at least one monomer of group (b), adding a polymerizationinitiator and polymerizing the mixture to completion. The graftpolymerization may also be carried out semicontinuously by firstintroducing a portion, for example 10%, of the mixture of polyalkyleneoxide to be polymerized, at least one monomer of group (b) and/or (c)and initiator, heating to polymerization temperature and, after thepolymerization has started, adding the remainder of the mixture to bepolymerized at a rate commensurate with the rate of polymerization. Thefirst graft copolymer may also be obtained by introducing thepolyalkylene oxides of group (a) into a reactor, heating to thepolymerization temperature, and adding at least one monomer of group (b)and/or (c) and polymerization initiator, either all at once, a little ata time, or uninterruptedly, optionally uninterruptedly, andpolymerizing.

In the preparation of the first graft copolymer, the order in which themonomers (b) and (c) are grafted onto component (a) may be immaterialand/or freely chooseable. For example, first N-vinylpyrrolidone may begrafted onto component (a), and then a monomer (c) or a mixture ofmonomers of group (c). It is also possible to first graft the monomersof group (c) and then N-vinylpyrrolidone onto the graft base (a). It maybe that a monomer mixture of (b) and (c) are grafted onto graft base (a)in one step. The first graft copolymer may be prepared by providinggraft base (a) and then first grafting N-vinylpyrrolidone and then vinylacetate onto the graft base.

Any suitable polymerization initiator(s) may be used, which may includeorganic peroxides such as diacetyl peroxide, dibenzoyl peroxide,succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate,tert-butyl perpivalate, tert-butyl permaleate, cumene hydroperoxide,diisopropyl peroxodicarbamate, bis(o-toluoyl) peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butylperisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butylperacetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, mixturesthereof, redox initiators, and/or azo starters. The choice of initiatormay be related to the choice of polymerization temperature.

The graft polymerization may take place at from 50° C. to 200° C., orfrom 70° C. to 140° C. The graft polymerization may typically be carriedout under atmospheric pressure, but may also be carried out underreduced or superatmospheric pressure.

The graft polymerization may be carried out in a solvent. Suitablesolvents may include: monohydric alcohols, such as ethanol, propanols,and/or butanols; polyhydric alcohols, such as ethylene glycol and/orpropylene glycol; alkylene glycol ethers, such as ethylene glycolmonomethyl and -ethyl ether and/or propylene glycol monomethyl and-ethyl ether; polyalkylene glycols, such as di- or tri-ethylene glycoland/or di- or tri-propylene glycol; polyalkylene glycol monoethers, suchas poly(C2-C3-alkylene)glycol mono (C1-C16-alkyl)ethers having 3-20alkylene glycol units; carboxylic esters, such as ethyl acetate andethyl propionate; aliphatic ketones, such as acetone and/orcyclohexanone; cyclic ethers, such as tetrahydrofuran and/or dioxane; ormixtures thereof.

The graft polymerization may also be carried out in water as solvent. Insuch cases, the first step may be to introduce a solution which,depending on the amount of added monomers of component (b), is more orless soluble in water. To transfer water-insoluble products that canform during the polymerization into solution, it is possible, forexample, to add organic solvents, for example monohydric alcohols having1 to 3 carbon atoms, acetone, and/or dimethylformamide. In a graftpolymerization process in water, it is also possible to transfer thewater-insoluble graft copolymers into a finely divided dispersion byadding customary emulsifiers or protective colloids, for examplepolyvinyl alcohol. The emulsifiers used may be ionic or nonionicsurfactants whose HLB value is from 3.0 to 13. HLB value is determinedaccording to the method described in the paper by W. C. Griffin in J.Soc. Cosmet. Chem. 5 (1954), 249.

The amount of surfactant used in the graft polymerization process may befrom 0.1 to 5.0% by weight of the graft copolymer. If water is used asthe solvent, solutions or dispersions of graft copolymers may beobtained. If solutions of graft copolymers are prepared in an organicsolvent or in mixtures of an organic solvent and water, the amount oforganic solvent or solvent mixture used per 100 parts by weight of thegraft copolymer may be from 5 to 200, optionally from to 100, parts byweight.

After the graft polymerization, the graft copolymer may optionally besubjected to a partial hydrolysis. In the graft copolymer, from 1.0 mol% to 60 mol %, preferably from 20 mol % to 60 mol %, more preferablyfrom 30 mol % to 50 mol % of the grafted-on monomers of component (c)are hydrolyzed. For instance, the hydrolysis of graft copolymersprepared using vinyl acetate or vinyl propionate as component (c) givesgraft copolymers containing vinyl alcohol units. The hydrolysis may becarried out, for example, by adding a base, such as sodium hydroxidesolution or potassium hydroxide solution, or alternatively by addingacids and if necessary, heating the mixture.

Second Graft Copolymer

The laundry composition according to the present application maycomprise a second graft copolymer comprising: a) polyalkylene oxidecomponent as a graft base; and b) polyvinyl ester component as sidechains. The second graft copolymer can be present at a level of fromabout to about 15%, preferably from about 0.05% to about 10%, morepreferably from about 0.1% to about 5%, and most preferably from about0.2% to about 3%, e.g. 0.1%, 0.15%, 0.2%, 0.25%, 0.35%, 0.4%, 0.45%,0.5%, 1%, 2%, or 3%, by weight of the composition.

Preferably, the second graft copolymer has an average of greater than 0to less than or equal to 1 graft site per 50 alkylene oxide units,and/or the second graft copolymer has from 20% to 70%, preferably from25% to 60%, by weight of said polymer of the polyalkylene oxidecomponent and from 30% to 80%, preferably from 40% to 75%, by weight ofsaid polymer of the vinyl ester component, and/or the second graftcopolymer has a mean molar mass Mw of from 3,000 to 60,000, preferablyfrom 6,000 to 45,000; and/or the second graft copolymer has apolydispersity of less than or equal to 3; and/or the second graftcopolymer comprises less than or equal to 10% by weight of the polyvinylester in ungrafted form.

The polyalkylene oxide backbone of the second graft copolymer of thepresent invention, which is also referred to herein as the graft base,may comprise repeated units of C₂-C₁₀, preferably C₂-C₆, and morepreferably C₂-C₄, alkylene oxides. For example, the polyalkylene oxidebackbone may be: a polyethylene oxide (PEO) backbone; a polypropyleneoxide (PPO) backbone; a polybutylene oxide (PBO) backbone; a polymericbackbone that is a linear block copolymer of PEO, PPO, and/or PBO; andcombinations thereof. Preferably, the polyalkylene oxide backbone is aPEO backbone.

The second graft co-polymer(s) comprises (i) a polyalkylene oxidebackbone; and (ii) at least one pendant moiety selected from polyvinylesters of saturated C₁- to C₁₄-carboxylic acid, acrylic and ormethacrylic esters of saturated monohydric alcohols contain 1 to 4carbon atoms, and mixtures thereof. The polyalkylene oxide backbone isobtained by polymerization of at least one monomer selected from groupconsisting of: ethylene oxide, propylene oxide, butylene oxide. Thepolyalkylene oxide backbone preferably comprises predominantly ethyleneoxide monomer units. Preferably, at least 50 mol %, more preferably atleast 80 mol %, most preferably at least 90 mol % of the monomer unitsof the polyalkylene oxide backbone are obtained from ethylene oxidemonomer units. The polyalkylene oxide backbone is particularlypreferably obtained by the polymerization of ethylene oxide. Thealkylene oxide units can be randomly distributed in the polymer or maybe present in the form of blocks. Examples of such polymers being blockcopolymers of ethylene oxide and propylene oxide, of ethylene oxide andbutylene oxide and of ethylene oxide, propylene oxide and butyleneoxide.

The polyalkylene oxide backbone can have a number average molecularweight of from 500 Da to 100,000 Da, preferably from 2,000 Da to from75,000 Da, more preferably from 4,000 Da to from 50,000 Da, mostpreferably from 4,000 Da to 20, 000 Da.

Preferably, the pendant moiety is derived from vinyl esters. Suitablevinyl esters are for example vinyl formate, vinyl acetate, vinylpropionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyli-valerate, vinyl laurate and vinyl caprolate. Preferably, the vinylester is vinyl acetate. It is maybe possible that up to 15% of the estergroups of the second graft co-polymer may be hydrolyzed.

Typically, the weight ratio of the polyalkylene oxide backbone topendant is between 10:90 and 90:10, preferably from 20:80 to 80:20, morepreferably from 30:70 to 70:30.

Polyethylene oxide having a number average molecular weight of from 2000to 100,000, in particular from 4000 to 50,000, is preferably used as thegrafting base. Up to 15% of the acetate groups of the graft copolymermay be hydrolyzed. Hydrolysis of the graft copolymers, which leads tograft copolymers containing vinyl alcohol units, is carried out byadding a base, such as NaOH or KOH, or an acid, and, if required,heating the mixture. The graft copolymers can have a K value accordingto H. Fikentscher of from 10 to 200, preferably from 20 to 100(determined in a 1% strength by weight solution in ethyl acetate at 25°C.).

As such, a suitable second graft copolymers is polyvinyl acetate graftedpolyethylene oxide copolymer, having a polyethylene oxide backbone andmultiple polyvinyl acetate side chains. The molecular weight of thepolyethylene oxide backbone is preferably from 4000 to 8000, morepreferably about 6000, and the weight ratio of the polyethylene oxide topolyvinyl acetate is 40:60, and less than or equal to 1 grafting pointper 50 ethylene oxide units. An example of such second graft co-polymersis Sokalan HP22, supplied from BASF.

Suitable second graft polymers are obtainable by grafting pendant groupssuch as vinyl acetate onto the polyalkylene oxide backbone, with thegraft copolymerization being initiated by free radicals. For thispurpose, it is possible either to use conventional polymerizationinitiators which decompose into free radicals under the polymerizationconditions or to initiate the polymerization by high energy radiation.Examples of processes for making suitable graft copolymers are disclosedin U.S. Pat. No. 4,746,456A.

Perfume

The detergent composition may comprise a perfume. Particularly, theperfume is in a format of a non-encapsulated perfume. The perfume can bepresent at a level of from about 0.001% to about 10%, preferably fromabout 0.005% to about 8%, more preferably from about 0.01% to about 5%,and most preferably from about 0.1% to about 2%, e.g. 0.1%, 0.15%, 0.2%,0.25%, 0.35%, 0.4%, 0.45%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, orany ranges therebetween, by weight of the composition.

Preferably, the perfume may have a ClogP of from about −2.0 and to about8.0, more preferably a ClogP of from about 1.0 and to about 6.0; morepreferably a ClogP of from about 1.0 and to about 4.0, for example 1.0,2.0, 3.0, 4.0, 5.0, 6.0 or any ranges thereof.

Perfume in the present application may be present in a form of neatperfume (e.g. perfume oil), perfume encapsulates (e.g. perfumemicrocapsule), a non-encapsulated fragrance delivery systems (e.g.properfumes) or any mixtures thereof.

In some embodiments, the perfume is selected from the group consistingof geraniol; menthol; (E,Z)-2,6-nonadien-1-ol; 3,6-nonadien-1-ol;2,2-dimethyl-3-(3-methylphenyl)propan-1-ol;2-methyl-3-[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]propan-1-ol;2-methyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-(2E)-buten-1-ol;ethyl trimethylcyclopentene butenol; 1-(4-propan-2-ylcyclohexyl)ethanol;1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;(Z)-3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pent-4-en-2-ol;undecavertol; methyl dihydrojasmonate; (E,Z)-2,6-nonadien-1-al;cashmeran; iso cyclo citral; triplal; neobutenone alpha; deltadamascone; alpha-pinyl isobutyraldehyde; vanillin; lilial; intrelevenaldehyde; hexyl cinnamic aldehyde; adoxal; dupical; lyral; 2-tridecenal;methyl-nonyl-acetaldehyde; 4-tert-butylbenzaldehyde; dihydrocitronellal;citral; citronellal; isocyclocitral; 2,4,6-trimethoxybenzaldehyde;cuminic aldehyde; 2-methyloctanal; para tolyl acetaldehyde;o-anisaldehyde; anisic aldehyde; hexyl aldehyde; 2-methylpenanal;benzaldehyde; trans-2-hexenal; nonyl aldehyde; lauric aldehyde; betaionone; koavone; tabanone coeur; zingerone; L-carvone; ionone gammamethyl; nectaryl; trimofix; farnesol;(E)-2-ethyl-4-(2,2,3-trimethyl-1-cyclopent-3-enyl)but-2-en-1-ol;2-Methyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-(2E)-buten-1-ol;nerol (800); ethyl vanillin;4-(5,5,6-Trimethylbicyclo[2.2.1]hept-2-yl)cyclohexan-1-ol; octalynol967544;(E)-3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol;3-methyl-4-phenylbutan-2-ol; eugenol;1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; propenyl guaethol;2-ethoxy-4-methylphenol; cyclopentol HC 937165;3,7,11-Trimethyl-1,6,10-dodecatrien-3-ol; cedrol crude;3,7-dimethyl-1,6-nonadien-3-ol (cis & trans);1-methyl-3-(2-methylpropyl)cyclohexanol;3,7-dimethyl-1,6-octadiene-3-ol;2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol;cyclohexanepropanol,2,2-dimethyl-, 3,7-dimethyl-1-octen-7-ol; Methylionone; isojasmone B 11; alpha-damascone; beta-damascone; fleuramone;3-ethoxy-4-hydroxybenzaldehyde; formyltricyclodecan; 6-methoxydicyclopentadiene carboxaldehyde; undecylenic aldehyde;4-hydroxy-3-methoxybenzaldehyde; 8-,9 and 10-undecenal, mixture ofisomers; trans-4-decenal; 4-dodecenal;4-(octahydro-4,7-methano-5H-inden-5-yliden)butanal;3-cyclohexene-1-propanal; beta, 4-dimethyl-, mandarine aldehyde 10% CITR965765; 4,8-dimethyl-4,9-decadienal; 1-methylethyl-2-methylbutanoate;ethyl-2-methyl pentanoate; 1,5-dimethyl-1-ethenylhexyl-4-enyl acetate;p-metnh-1-en-8-yl acetate;4-(2,6,6-trimethyl-2-cyclohexenyl)-3-buten-2-one;4-acetoxy-3-methoxy-1-propenylbenzene; 2-propenyl cyclohexanepropionate;bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, 3-(1-methylethyl)-ethylester; bycyclo [2.2.1]heptan-2-ol, 1,7,7-trimethyl-, acetate;1,5-dimethyl-1-ethenylhex-4-enylacetate; hexyl 2-methyl propanoate;ethyl-2-methylbutanoate; 4-undecanone; 5-heptyldihydro-2(3h)-furanone;1,6-nonadien-3-o1,3,7dimethyl-; 3,7-dimethylocta-1,6-dien-3-o;3-cyclohexene-1-carboxaldehyde, dimethyl-; 3,7-dimethyl-6-octenenitrile; 4-(2,6,6-trimethyl-1-cyclohexenyl)-3-buten-2-one;tridec-2-enonitrile; patchouli oil; ethyl tricycle[5.2.1.0]decan-2-carboxylate; 2,2-dimethyl-cyclohexanepropanol; hexylethanoate, 7-acetyl,1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphtalene; allyl-cyclohexyloxy acetate; methyl nonyl acetic aldehyde;1-spiro[4,5]dec-7-en-7-yl-4-pentenen-1-one;7-octen-2-o1,2-methyl-6-methylene-,dihydro;cyclohexanol,2-(1,1-dimethylethyl)-, acetate;hexahydro-4,7-methanoinden-5(6)-ylpropionatehexahydro-4,7-methanoinden-5(6)-yl propionate;2-methoxynaphtalene; 1-(2,6,6-trimethyl-3-cyclohexenyl)-2-buten-1-one;1-(2,6,6-trimethyl-2-cyclohexenyl)-2-buten-1-one;3,7-dimethyloctan-3-ol;3-buten-2-one,3-methyl-4-(2,6,6-trimehtyl-1-cyclohexen-2-yl)-; hexanoicacid, 2-propenyl ester; (z)-non-6-en-1-al; 1-decyl aldehyde; 1-octanal;4-t-butyl-α-methylhydrocinnamaldehyde; alpha-hexylcinnamaldehyde;ethyl-2,4-hexadienoate; 2-propenyl 3-cyclohexanepropanoate;(5-methyl-2-propan-2-ylcyclohexyl) acetate; 3,7-dimethyloct-6-en-1-al;2-(phenoxy)ethyl 2-methylpropanoate; prop-2-enyl2-(3-methylbutoxy)acetate; 3-methyl-1-isobutylbutyl acetate; prop-2-enylhexanoate; prop-2-enyl 3-cyclohexylpropanoate; prop-2-enyl heptanoate;(E)-1-(2,6,6-trimethyl-1-cyclohex-2-enyl)but-2-en-1-one;(E)-4-(2,6,6-trimethyl-1-cyclohex-2-enyl)but-3-en-2-one;(E)-3-methyl-4-(2,6,6-trimethyl-1-cyclohex-2-enyl)but-3-en-2-one;1-(2,6,6-trimethyl-1-cyclohex-2-enyl)pent-1-en-3-one;6,6,9a-trimethyl-1,2,3a,4,5,5a,7,8,9,9b-decahydronaphtho[2,1-Nfuran;pentyl 2-hydroxybenzoate; 7,7-dimethyl-2-methylidene-norbornane;(E)-1-(2,6,6-trimethyl-1-cyclohexenyl)but-2-en-1-one;(E)-4-(2,6,6-trimethyl-1-cyclohexenyl)but-3-en-2-one;4-ethoxy-4,8,8-trimethyl-9-methylidenebicyclo[3.3.1]nonane;(1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl) acetate;3-(4-tert-butylphenyl)propanal;1,1,2,3,3-pentamethyl-2,5,6,7-tetrahydroinden-4-one;2-oxabicyclo2.2.2octane, 1methyl4(2,2,3trimethylcyclopentyl);[(Z)-hex-3-enyl]acetate; [(Z)-hex-3-enyl] 2-methylbutanoate;cis-3-hexenyl 2-hydroxybenzoate; 3,7-dimethylocta-2,6-dienal;3,7-dimethyloct-6-en-1-al; 3,7-dimethyl-6-octen-1-ol;3,7-dimethyloct-6-enyl acetate; 3,7-dimethyloct-6-enenitrile;2-(3,7-dimethyloct-6-enoxy)acetaldehyde;tetrahydro-4-methyl-2-propyl-2h-pyran-4-yl acetate; ethyl3-phenyloxirane-2-carboxylate; hexahydro-4,7-methano-indenylisobutyrate; 2,4-dimethylcyclohex-3-ene-1-carbaldehyde;hexahydro-4,7-methano-indenyl propionate; 2-cyclohexylethyl acetate;2-pentylcyclopentan-1-ol;(2R,3R,4S,5S,6R)-2-R2R,3S,4R,5R,6R)-6-(6-cyclohexylhexoxy)-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol;(E)-1-(2,6,6-trimethyl-1-cyclohexa-1,3-dienyl)but-2-en-1-one;1-cyclohexylethyl (E)-but-2-enoate; dodecanal;(E)-1-(2,6,6-trimethyl-1-cyclohex-3-enyl)but-2-en-1-one;(5E)-3-methylcyclopentadec-5-en-1-one;4-(2,6,6-trimethyl-1-cyclohex-2-enyl)butan-2-one; 2-methoxy-4-propylphenol; methyl 2-hexyl-3-oxocyclopentane-1-carboxylate;2,6-dimethyloct-7-en-2-ol; 4,7-dimethyloct-6-en-3-one;4-(octahydro-4,7-methano-5H-inden-5-yliden)butanal; acetaldehyde ethyllinalyl acetal; ethyl 3,7-dimethyl-2,6-octadienoate; ethyl2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate; 2-ethylhexanoate;(6E)-3,7-dimethylnona-1,6-dien-3-ol; ethyl 2-methylbutanoate; ethyl2-methylpentanoate; ethyl tetradecanoate; ethyl nonanoate; ethyl3-phenyloxirane-2-carboxylate; 1,4-dioxacycloheptadecane-5,17-dione;1,3,3-trimethyl-2-oxabicyclo[2,2,2]octane; [essential oil];oxacyclo-hexadecan-2-one; 3-(4-ethylphenyl)-2,2-dimethylpropanal;2-butan-2-ylcyclohexan-1-one; 1,4-cyclohexandicarboxylic acid, diethylester;(3aalpha,4beta,7beta,7aalpha)-octahydro-4,7-methano-3aH-indene-3a-carboxylicacid ethyl ester; hexahydro-4-7, menthano-1H-inden-6-yl propionate;2-butenon-1-one,1-(2,6-dimethyl-6-methylencyclohexyl)-;(E)-4-(2,2-dimethyl-6-methylidenecyclohexyl)but-3-en-2-one;1-methyl-4-propan-2-ylcyclohexa-1,4-diene; 5-heptyloxolan-2-one;3,7-dimethylocta-2,6-dien-1-ol; [(2E)-3,7-dimethylocta-2,6-dienyl]acetate; [(2E)-3,7-dimethylocta-2,6-dienyl] octanoate; ethyl2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate;(4-methyl-1-propan-2-yl-1-cyclohex-2-enyl) acetate;2-butyl-4,6-dimethyl-5,6-dihydro-2H-pyran; oxacyclohexadecen-2-one;1-propanol,2-[1-(3,3-dimethyl-cyclohexyl)ethoxy]-2-methyl-propanoate;1-heptyl acetate; 1-hexyl acetate; hexyl 2-methylpropanoate;(2-(1-ethoxyethoxy)ethyl)benzene;4,4a,5,9b-tetrahydroindeno[1,2-d][1,3]dioxine; undec-10-enal;3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one;1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one;7-acetyl,1,2,3,4,5,6,7-octahydro-1,1,6,7,-tetra methyl naphthalene;3-methylbutyl 2-hydroxybenzoate;[(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate;R1R,4R,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] 2-methylpropanoate;(1,7,7-trimethyl-5-bicyclo[2.2.1]heptanyl) propanoate; 2-methylpropylhexanoate; [2-methoxy-4-RE)-prop-1-enyl]phenyl] acetate;2-hexylcyclopent-2-en-1-one; 5-methyl-2-propan-2-ylcyclohexan-1-one;7-methyloctyl acetate; propan-2-yl 2-methylbutanoate;3,4,5,6,6-pentamethylheptenone-2;hexahydro-3,6-dimethyl-2(3H)-benzofuranone;2,4,4,7-tetramethyl-6,8-nonadiene-3-one oxime; dodecyl acetate;[essential oil]; 3,7-dimethylnona-2,6-dienenitrile; [(Z)-hex-3-enyl]methyl carbonate; 2-methyl-3-(4-tert-butylphenyl)propanal;3,7-dimethylocta-1,6-dien-3-ol; 3,7-dimethylocta-1,6-dien-3-yl acetate;3,7-dimethylocta-1,6-dien-3-yl butanoate; 3,7-dimethylocta-1,6-dien-3-ylformate; 3,7-dimethylocta-1,6-dien-3-yl 2-methylpropanoate;3,7-dimethylocta-1,6-dien-3-yl propanoate;3-methyl-7-propan-2-ylbicyclo[2.2.2]oct-2-ene-5-carbaldehyde;2,2-dimethyl-3-(3-methylphenyl)propan-1-ol;3-(4-tert-butylphenyl)butanal; 2,6-dimethylhept-5-enal;5-methyl-2-propan-2-yl-cyclohexan-1-ol;1-(2,6,6-trimethyl-1-cyclohexenyl)pent-1-en-3-one; methyl3-oxo-2-pentylcyclopentaneacetate; methyl tetradecanoate;2-methylundecanal; 2-methyldecanal;1,1-dimethoxy-2,2,5-trimethyl-4-hexene;R1S)-3-(4-methylpent-3-enyl)-1-cyclohex-3-enyl]methyl acetate;2-(2-(4-methyl-3-cyclohexen-1-yl)propyl)cyclo-pentanone; 4-penten-1-one,1-(5,5-dimethyl-1-cyclohexen-1-yl;1H-indene-ar-propanal,2,3,-dihydro-1,1-dimethyl-(9CI);2-ethoxynaphthalene; nonanal;2-(7,7-dimethyl-4-bicyclo[3.1.1]hept-3-enyl)ethyl acetate; octanal;4-(1-methoxy-1-methylethyl)-1-methylcyclohexene;(2-tert-butylcyclohexyl) acetate;(E)-1-ethoxy-4-(2-methylbutan-2-yl)cyclohexane; 1,1-dimethoxynon-2-yne;[essential oil]; 2-cyclohexylidene-2-phenylacetonitrile;2-cyclohexyl-1,6-heptadien-3-one; 4-cyclohexyl-2-methylbutan-2-ol;2-phenylethyl 2-phenylacetate; (2E, 5E/Z)-5,6,7-trimethylocta-2,5-dien-4-one;1-methyl-3-(4-methylpent-3-enyl)cyclohex-3-ene-1-carbaldehyde; methyl2,2-dimethyl-6-methylidenecyclohexane-1-carboxylate;1-(3,3-dimethylcyclohexyl)ethyl acetate;4-methyl-2-(2-methylprop-1-enyl)oxane;1-spiro(4.5)-7-decen-7-yl-4-penten-1-one;4-(2-butenylidene)-3,5,5-trimethylcyclohex-2-en-1-one;2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol;4-isopropylidene-1-methyl-cyclohexene;2-(4-methyl-1-cyclohex-3-enyl)propan-2-yl acetate;3,7-dimethyloctan-3-ol; 3,7-dimethyloctan-3-ol; 3,7-dimethyloctan-3-ylacetate; 3-phenylbutanal; (2,5-dimethyl-4-oxofuran-3-yl) acetate;4-methyl-3-decen-5-ol; undec-10-enal; (4-formyl-2-methoxyphenyl)2-methylpropanoate; 2,2,5-trimethyl-5-pentylcyclopentan-1-one;2-tert-butylcyclohexan-1-ol; (2-tert-butylcyclohexyl) acetate;4-tert-butylcyclohexyl acetate;1-(3-methyl-7-propan-2-yl-6-bicyclo[2.2.2]oct-3-enyl)ethanone;(4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulen-6-yl)acetate; [(4Z)-1-cyclooct-4-enyl] methyl carbonate; methyl beta naphtylether; and any mixtures thereof.

Dye Transfer Inhibitors

The detergent composition may further comprise one or more dye transferinhibitors (DTI) polymers. The DTI polymer can be present at the levelof from about 0.001% to about 1%, preferably from about 0.005% to about0.5%, more preferably from about 0.008% to about 0.2%, and mostpreferably from about 0.01% to about 0.1%, e.g. 0.01%, 0.015%, 0.02%,0.025%, 0.03%, 0.035%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.1% or anyranges therebetween, by weight of the composition, of the DTI polymer

Suitable dye transfer inhibitors are selected from the group consistingof: polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones, polyvinylimidazoles and mixtures thereof. Othersuitable DTIs are triazines as described in WO2012/095354, polymerizedbenzoxazines as described in WO2010/130624, polyvinyl tetrazoles asdescribed in DE 102009001144A, porous polyamide particles as describedin WO2009/127587 and insoluble polymer particles as described inWO2009/124908. Other suitable DTIs are described in WO2012/004134, orpolymers selected from the group consisting of (a) amphiphilicalkoxylated polyamines, amphiphilic graft co-polymers, zwitterionic soilsuspension polymers, manganese phthalocyanines, peroxidases and mixturesthereof.

Preferred classes of DTI include but are not limited topolyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones,polyvinylimidazoles and mixtures thereof. More specifically, thepolyamine N-oxide polymers preferred for use herein contain units havingthe following structural formula: R-AX-P; wherein P is a polymerizableunit to which an N—O group can be attached or the N—O group can formpart of the polymerizable unit or the N—O group can be attached to bothunits; A is one of the following structures: —NC(O)—, —C(O)O—, —S—, —O—,—N═; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,heterocyclic or alicyclic groups or any combination thereof to which thenitrogen of the N—O group can be attached or the N—O group is part ofthese groups. Preferred polyamine N-oxides are those wherein R is aheterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,piperidine and derivatives thereof.

The N—O group can be represented by the following general structures:

-   -   wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or        alicyclic groups or combinations thereof; x, y and z are 0 or 1;        and the nitrogen of the N—O group can be attached or form part        of any of the aforementioned groups. The amine oxide unit of the        polyamine N-oxides has a pKa<10, preferably pKa<7, more        preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization.

Typically, the average molecular weight is within the range of 500 to1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to100,000. This preferred class of materials can be referred to as “PVNO”.The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as “PVPVI”) are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113.“Modem Methods of Polymer Characterization”). The PVPVI copolymerstypically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidonefrom 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferablyfrom to 0.4:1.

These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone (“PVP”) having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about to about 200,000,and more preferably from about 5,000 to about 50,000. PVP's are known topersons skilled in the detergent field; see, for example, EP-A-262,897and EP-A-256,696, incorporated herein by reference. Compositionscontaining PVP can also contain polyethylene glycol (“PEG”) having anaverage molecular weight from about 500 to about 100,000, preferablyfrom about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP ona ppm basis delivered in wash solutions is from about 2:1 to about 50:1,and more preferably from about 3:1 to about 10:1.

Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBondS-403E and Chromabond S-100 from Ashland, and Sokalan® HP165, Sokalan®HP50, Sokalan® HP53, Sokalan® HP59, Sokalan® HP 56K, Sokalan® HP 66 fromBASF; Reilline 4140 from Vertellus.

Surfactant System

Preferably, the composition may comprise from 4% to 80%, preferably from6% to 50%, more preferably from 10% to 30%, e.g., 5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45%, 50% or any ranges therebetween, by weight ofthe composition, of a surfactant system. Particularly, the surfactantsystem may comprise an anionic surfactant and a nonionic surfactant.

The anionic surfactant suitable for the composition in the presentinvention may be selected from the group consisting of C₆-C₂₀ linearalkylbenzene sulfonates (LAS), C₆-C₂₀ alkyl sulfates (AS), C₆-C₂₀ alkylalkoxy sulfates (AAS), C₆-C₂₀ methyl ester sulfonates (MES), C₆-C₂₀alkyl ether carboxylates (AEC), and any combinations thereof. Forexample, the laundry detergent composition may contain a C₆-C₂₀ alkylalkoxy sulfates (AA_(x)S), wherein x is about 1-30, preferably about1-15, more preferably about 1-10, most preferably x is about 1-3. Thealkyl chain in such AAXS can be either linear or branched, withmid-chain branched AAXS surfactants being particularly preferred. Apreferred group of AA_(x)S include C₁₂-C₁₄ alkyl alkoxy sulfates with xof about 1-3. In some embodiments, the composition comprises from 1% to30%, preferably from 2% to 25%, more preferably from 3% to 20%, forexample, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, or anyranges therebetween, by weight of the composition of the anionicsurfactant.

The nonionic surfactant suitable for the composition in the presentinvention may be selected from the group consisting of alkyl alkoxylatedalcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxyfatty acid amides, alkoxylated fatty acid esters, sucrose esters,sorbitan esters and alkoxylated derivatives of sorbitan esters, and anycombinations thereof. Non-limiting examples of nonionic surfactantssuitable for use herein include: C₁₂-C₁₈ alkyl ethoxylates, such asNeodol® nonionic surfactants available from Shell; C₆-C₁₂ alkyl phenolalkoxylates wherein the alkoxylate units are a mixture of ethyleneoxyand propyleneoxy units; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenolcondensates with ethylene oxide/propylene oxide block alkyl polyamineethoxylates such as Pluronic® available from BASF; C₁₄-C₂₂ mid-chainbranched alkyl alkoxylates, BAEx, wherein x is from about 1 to about 30;alkylpolysaccharides, specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants. Also useful herein as nonionic surfactants are alkoxylatedester surfactants such as those having the formula R¹C(O)O(R₂O)_(n)R³wherein R¹ is selected from linear and branched C₆-C₂₂ alkyl or alkylenemoieties; R² is selected from C₂H₄ and C₃H₆ moieties and R³ is selectedfrom H, CH₃, C₂H₅ and C₃H₇ moieties; and n has a value between about 1and about 20. Such alkoxylated ester surfactants include the fattymethyl ester ethoxylates (MEE) and are well-known in the art. In someparticular embodiments, the alkoxylated nonionic surfactant contained bythe laundry detergent composition of the present invention is a C₆-C₂₀alkoxylated alcohol, preferably C₅-C₁₈ alkoxylated alcohol, morepreferably C₁₀-C₁₆ alkoxylated alcohol. The C₆-C₂₀ alkoxylated alcoholis preferably an alkyl alkoxylated alcohol with an average degree ofalkoxylation of from about 1 to about 50, preferably from about 3 toabout 30, more preferably from about 5 to about even more preferablyfrom about 5 to about 9. In some embodiments, the composition comprisesfrom 1% to 30%, preferably from 2% to 25%, more preferably from 3% to20%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%,or any ranges therebetween, by weight of the composition of the nonionicsurfactant.

The ratio of anionic surfactant to nonionic surfactant may be between0.01 and 100, preferably between 0.05 and 20, more preferably between0.1 and 10, and most preferably between and 5.

In some embodiments, the anionic surfactant comprises a C₆-C₂₀ linearalkylbenzene sulfonate surfactant (LAS), preferably C₁₀-C₁₆ LAS, andmore preferably C₁₂-C₁₄ LAS. In some particular embodiments of thepresent invention, the anionic surfactant may be present as the mainsurfactant, preferably as the majority surfactant, in the composition.Preferably, the ratio of anionic surfactant to nonionic surfactant maybe between 1.05 and 100, preferably between 1.1 and 20, more preferablybetween 1.2 and 10, and most preferably between 1.3 and 5. Particularly,the anionic surfactant may comprise C₆-C₂₀ linear alkylbenzenesulfonates (LAS).

In some particular embodiments of the present invention, the nonionicsurfactant may be present as the main surfactant, preferably as themajority surfactant, in the composition. Preferably, the ratio ofanionic surfactant to nonionic surfactant may be between 0.01 and 0.95,preferably between 0.05 and 0.9, more preferably between 0.1 and 0.85,and most preferably between 0.2 and Particularly, the nonionicsurfactant may comprise C₆-C₂₀ alkoxylated alcohol.

The laundry detergent composition of the present invention may furthercomprise a cationic surfactant. Non-limiting examples of cationicsurfactants include: quaternary ammonium surfactants, which can have upto 26 carbon atoms include: alkoxylate quaternary ammonium (AQA)surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants;and amino surfactants, specifically amido propyldimethyl amine (APA).

The laundry detergent composition of the present invention may furthercomprise an amphoteric surfactant. Non-limiting examples of amphotericsurfactants include: amine oxides, derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Preferred examples include: C₆-C₂₀ alkyldimethylamine oxides, betaine, including alkyl dimethyl betaine and cocodimethylamidopropyl betaine, sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈-C₁₈ or C₁₀-C₁₄.

Other Ingredients

The laundry detergent composition of the present invention may furthercomprise a cationic surfactant. Non-limiting examples of cationicsurfactants include: quaternary ammonium surfactants, which can have upto 26 carbon atoms include: alkoxylate quaternary ammonium (AQA)surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants;and amino surfactants, specifically amido propyldimethyl amine (APA).

The laundry detergent composition herein may comprise adjunctingredients. Suitable adjunct materials include but are not limited to:builders, chelating agents, rheology modifiers, dye transfer inhibitingagents, dispersants, enzymes, and enzyme stabilizers, anti-oxidants,catalytic materials, bleach activators, hydrogen peroxide, sources ofhydrogen peroxide, preformed peracids, polymeric dispersing agents, claysoil removal/anti-redeposition agents, brighteners, suds suppressors,dyes, photobleaches, perfumes, perfume microcapsules, structureelasticizing agents, fabric softeners, carriers, hydrotropes, processingaids, solvents, hueing agents, structurants and/or pigments. The precisenature of these adjunct ingredients and the levels thereof in thelaundry detergent composition will depend on the physical form of thecomposition and the nature of the cleaning operation for which it is tobe used.

In some embodiments, the laundry detergent composition according to thepresent disclosure may further comprise from 0.01% to 10%, preferablyfrom 0.1% to 5%, more preferably from 0.2% to 4%, most preferably from0.3% to 3%, for example, 0.5%, 1%, 2%, 3%, 4%, 5% or any ranges thereof,by weight of the composition, of a fatty acid.

Composition Preparation

The laundry detergent composition of the present invention is generallyprepared by conventional methods such as those known in the art ofmaking laundry detergent compositions. Such methods typically involvemixing the essential and optional ingredients in any desired order to arelatively uniform state, with or without heating, cooling, applicationof vacuum, and the like, thereby providing laundry detergentcompositions containing ingredients in the requisite concentrations.

Method of Use

Another aspect of the present invention is directed to a method of usingthe laundry detergent composition to treat a fabric. Such method candeliver a color protection benefit. The method comprises the step ofadministering from 5 g to 120 g of the above-mentioned laundry detergentcomposition into a laundry washing basin comprising water to form awashing solution. The washing solution in a laundry washing basin hereinpreferably has a volume from 1 L to 65 L, alternatively from 1 L to 50L, alternatively from 1 L to 20 L for hand washing and from 10 L to 50 Lfor machine washing. The temperatures of the laundry washing solutionpreferably range from 5° C. to 60° C.

In some embodiments, the composition is added to a washing machine via adispenser (e.g. a dosing drawer). In some other embodiments, thecomposition is added to an automatic dosing washing machine via anautomatic dosing mechanism. In some other embodiments, the compositionis added to directly a drum of a washing machine. In some otherembodiments, the composition is added directly to the wash liquor.

The dosing amount in the method herein may be different depending on thewashing type. In one embodiment, the method comprises administering fromabout 5 g to about 60 g of the laundry detergent composition into a handwashing basin (e.g., about 2-4 L). In an alternative embodiment, themethod comprises administering from about 5 g to about 100 g, preferablyfrom about 10 g to about 65 g of the laundry detergent composition intoa washing machine (e.g., about L).

Test Method Test 1: Perfume Deposition Test

Before testing for perfume deposition, the test fabrics are prepared andtreated according to the procedure described below. Fabrics aretypically “de-sized” and/or “stripped” of any manufacturer's finish thatmay be present and pre-conditioned with fabric enhancer according to A,dried, cut into fabric specimens and then treated with a detergentcomposition in a tergotometer.

A. Fabric Preparation Method.

Fabrics may be prepared according to one or both of the followingmethods.

A1. Fabric De-sizing Method. New fabrics are de-sized by washing twocycles at 49° C. (120° F.), using zero grain water in a top loadingwashing machine such as Kenmore 80 series. All fabrics are tumble-driedafter the second cycle for 45 minutes on cotton/high setting in aKenmore series dryer.

A2. Fabric Pre-conditioning Method. De-sized fabrics are pre-conditionedwith detergent and liquid fabric softener by washing for 3 cycles at 32°C. using 6 grain per gallon water in a top loading washing machine suchas Kenmore 80 series. The detergent (Tide®, 83 g) is added to the drumof the washing machine after the water has filled at the beginning ofthe wash cycle, followed by 2.5 kg of de-sized 100% cotton terry towels(30.5 cm×30.5 cm, RN37000-ITL available from Calderon Textiles, LLC6131W 80th St Indianapolis IN). Liquid fabric softener (Downy®, 46 g) isadded to the drum during the rinse cycle once the rinse water hasfilled. All fabrics are tumble-dried after the second cycle for 45minutes on cotton/high setting in a Kenmore series dryer. Each treatedfabric is die-cut into 1.4 cm-diameter circle test specimens using apneumatic press (Atom Clicker Press SE20 C available from ManufacturingSuppliers Services, Cincinnati, OH).

B. Fabric Treatment Method in a Tergotometer.

The tergotometer is filled to a 1 L fill volume and is programmed for a12 min agitation time, and a 10 min rinse cycle with an agitation speedof 300 rpm using 15 gpg/30° C. water for the wash and 15 gpg/25° C. (77°F.) water for the rinse with agitation sweep angle of 15°. Water isremoved by centrifugation for 2 min at 1500 rpm after the washing andrinsing steps. The Detergent Composition (1.5 g) is added to the washingpot after the water is filled to 350 g and then agitated for 60 s. Thepre-conditioned fabrics (8×1.4 cm diameter circles) are added to glasssample vial (#24694, available from Restek, Bellefonte, PA), the weightis recorded (8×1.4 cm circles weigh about 0.63 g±0.07 g), and the vialis capped (#093640-094-00 available from Gerstel, Linthicum, MD). Oncethe detergent, and all test fabrics are added to the Tergotometer pot,the timed cycle begins. After the washing cycle is complete, the fabricsare removed, and dried for 30 min/62° C. For each perfume depositionanalysis, 12 replicates are prepared according to the method above andanalyzed.

Fabric Perfume Deposition analysis is performed using Solid-phase MicroExtraction Gas Chromatography Mass Spectrometry (SPME GC-MS) describedbelow. Perfume deposition analysis is carried out on treated 100% cottonterry towels (RN37000ITL, Calderon Textiles, LLC, Indianapolis, IN, USA)that have been prepared and treated according to the fabric preparationmethod that is described above.

Perfume deposition analysis is done on 8 treated fabrics from 12different vials for a total of 96 fabrics divided into six vialscontaining treated fabrics from two replicates. Dried fabrics from tworeplicates are combined in a 20 mL VOA vial (#10854-102, available fromAvantor, Radnor, PA) for a total mass of about 1.25 g (±0.15 g) offabric in each of six vials. Perfume deposition results are reported asan average from these 6 vials.

The determination of the amount of perfume deposited onto treated fabricrequires the extraction of the perfume. The extraction of the perfume isperformed utilizing a liquid extraction followed by GC-MS quantificationdescribed above.

An equal mass of untreated fabric is spiked with a known amount of aknown perfume mixture and analyzed to create a multipoint calibration.The perfume is extracted from the treated fabrics in the sealedextraction vial using methanol (8 mL) and heat (35° C.) in a 45-minuteextraction. After 45 minutes, remove vials and vortex mix for 15 secondsat 2600 rpm. Vials are allowed to cool to room temperature. 500microliter aliquot of the methanol collected in VOA vials is added to4.5 mL of a 20% NaCl in deionized water solution (5 mL total solution)in a 20 mL headspace vial (#10854-102, available from Avantor, Radnor,PA).

The sample vials containing the 5 mL of solution are then loaded onto aGerstel MPS2 Autosampler (Gerstel Inc., Linthicum, MD, USA). Prior tothe headspace analysis, each sample is pre-conditioned in the machine at65° C. for 10 minutes. Headspace is extracted onto the Agilent7890B/5977A GC-MS system (Agilent Technologies, Santa Clara, CA, USA)equipped with a Supelco 100 micrometer PDMS 23Ga. Solid Phase MicroExtraction fiber (Supelco Inc., Bellefonte, PA, USA). GC analysis isconducted on a non-polar capillary column (DB-5MS UI, meters nominaldiameter, 0.25 millimeter nominal diameter, 25 micrometer thickness) andthe headspace constituents (i.e. the perfume raw materials) aremonitored by Mass Spectrometry (EI, detector). Perfume concentration iscalculated utilizing a multi-point calibration of the perfume rawmaterials from the spiked fabrics. The total deposition is the sum ofeach detected perfume raw material divided by the mass of the fabric.Deposition efficiency is calculated by dividing the extracted perfumeper gram of fabric by the total encapsulated perfume delivered to thewashing machine divided by the total mass of the fabric load and isreported as a percentage.

EXAMPLES Synthesis Example 1: Synthesis of Graft Copolymer

A polymerization vessel equipped with stirrer and reflux condenser wasinitially charged with 720 g of PEG (6000 g/mol) and 60 g 1,2-propanediol (MPG) under nitrogen atmosphere. The mixture was homogenized at 70°C.

Then, 432 g of vinyl acetate (in 2 h), 288 g of vinylpyrrolidone in 576g of MPG (in 5 h), and 30.2 g of tert.-butyl perpivalate in 196.6 g MPG(in 5.5 h) were metered in. Upon complete addition of the feeds, thesolution was stirred at 70° C. for 1 h. Subsequently, 3.8 g tert.-butylperpivalate in 25.0 g MPG (in 1.5 h) were metered in followed by 0.5 hof stirring.

The volatiles were removed by vacuum stripping. Then, 676.8 g deionizedwater were added and a steam distillation was conducted at 100° C. for 1h.

The temperature of the reaction mixture was reduced to 80° C. and 160.6g of aqueous sodium hydroxide solution (50%, 40 mol % respective VAc)was added with maximum feed rate. Upon complete addition of the sodiumhydroxide solution, the mixture was stirred for 1 h at 80° C. andsubsequently cooled to ambient temperature.

The resulting graft polymer is characterized by a K-value of 24. Thesolid content of the final solution is 45%.

Example 1: Improved Deposition of Perfume onto Fabrics by Adding TwoGraft Copolymers in Laundry Detergent Composition

Six (6) sample liquid laundry detergent compositions were preparedcontaining the following ingredients as shown in Table 1. Sample 1 doesnot contain any graft copolymer. Sample 2 contains the second graftcopolymer only. Samples 3 to 6 contain both the graft copolymer and thesecond graft copolymer according to the present application with thesame ratio (3:2) at different levels.

TABLE 1 Ingredients (weight %) Sample 1 Sample 2 Sample 3 Sample 4Sample 5 Sample 6 First Graft — — 0.34% 0.55% 1.09% 1.64% copolymer¹Second Graft — 0.57% 0.23% 0.36% 0.73% 1.09% copolymer² C₁₂-₁₄AE₁₋₃S3.0% 3.0% 3.0% 3.0% 3.0% 3.0% C₁₁-₁₃LAS 2.9% 2.9% 2.9% 2.9% 2.9% 2.9%C₁₂-₁₄EO₇ 2.7% 2.7% 2.7% 2.7% 2.7% 2.7% C₁₂-C₁₈ Fatty Acid 2.7% 2.7%2.7% 2.7% 2.7% 2.7% Perfume   1%   1%   1%   1%   1%   1% AdditionalBalance Balance Balance Balance Balance Balance ingredients (includingwater) ¹First Graft Copolymer: Graft copolymer described in SynthesisExample 1 with PVP/PVAc-g-PEG at 20:30:50 by weight ratio withweight-average MW 16,800 Dalton. ²Second Graft Copolymer: Polyvinylacetate grafted polyethylene oxide copolymer having a polyethyleneoxidebackbone and multiple polyvinyl acetate side chains, supplied by BASF,Germany.

In accordance with Test 1: Perfume Deposition Test as describedhereinabove, the content of perfume deposited onto fabrics washed byusing these samples were measured.

The results are shown in the table below, in which the liquid laundrydetergent compositions containing both the first and second graftcopolymers show significantly higher deposition of perfume on fabricsafter being washed compared to the liquid laundry detergent compositioncontaining only the second graft copolymer or no graft copolymer. Thisdiscovery is surprising because previous data shows the first graftcopolymer only cannot significantly improve the deposition of perfume onfabrics after being washed. Even more unexpectedly, Sample 3 containinga relatively low level of total graft copolymer (0.57%) showssurprisingly higher deposition of perfume compared to Sample 5 (1.8%) or6 (2.7%).

TABLE 2 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 a b c d ef Total perfume 18.2 25.6a 30.5aef 27.0f 25.1a 24.4a deposition (μg/g)Total copolymer — 0.57% 0.57% 0.91% 1.82% 2.73% content

Example 2: Exemplary Formulations of Laundry Detergent Compositions

The following liquid laundry detergent compositions as shown in Table 3ato 3c are made comprising the listed ingredients in the listedproportions (weight %).

TABLE 3a Ingredients (weight %) A B C D E F C₁₂-₁₄AE₁₋₃S 4 1.5 3 1 4 1.5C₁₁-₁₃LAS 2 3 5 1 2 3 C₁₄-₁₅EO₇ 10 8.5 15 12 5 — C₁₂-₁₄EO₇ — — — — — 8First Graft Copolymer¹ 0.05 0.09 0.17 0.13 0.15 0.29 Second GraftCopolymer² 0.02 0.05 0.10 0.12 0.08 0.29 Citric acid 2.4 0.5 4.8 0.6 — 2C₁₂-C₁₈ fatty acid 3.2 1.2 2.2 2 1.5 1.2 Na-DTPA 1 0.05 0.5 0.18 0.060.2 Sodium cumene sulphonate — — — 4.42 — — Ethanol — — — 1.74 — —Silicone emulsion — 0.0025 0.0025 0.0025 — 0.0025 Sodium polyacrylate1.4 — — — 1.4 — Polyethyleneimines — — 1.0 — — — NaOH Up to Up to Up toUp to Up to Up to pH 8 pH 8 pH 8 pH 8 pH 8 pH 8 Na Formate — — — 0.02 —— Protease — — 0.45 0.29 — — Amylase — — 0.08 — — — Dye — 0.002 0.0020.001 — 0.002 Perfume oil 0.2 0.6 0.6 0.57 0.1 0.6 Water Balance BalanceBalance Balance Balance Balance ¹First Graft Copolymer: Graft copolymerdescribed in Synthesis Example 1 with PVP/PVAc-g-PEG at 20:30:50 byweight ratio with weight-average MW 16,800 Dalton. ²Second GraftCopolymer: Polyvinyl acetate grafted polyethylene oxide copolymer havinga polyethyleneoxide backbone and multiple polyvinyl acetate side chains,supplied by BASF, Germany.

TABLE 3b Ingredients (weight %) G H I J K L C₁₂-₁₄AE₁₋₃S 9 10 12 3 4 1.5C₁₁-₁₃LAS 2 3 5 12 9 15 C₁₄-₁₅EO₇ 5 — — 3 — — C₁₂-₁₄EO₇ — 3 4 — 3 8First Graft Copolymer¹ 0.5 0.9 0.7 0.3 0.5 0.9 Second Graft Copolymer² 12 5 0.5 0.7 3 Citric acid 2.4 0.5 4.8 0.6 — 2 C₁₂-C₁₈ fatty acid 3.2 1.22.2 2 1.5 1.2 Na-DTPA 1 0.05 0.5 0.18 0.06 0.2 Sodium cumene sulphonate— — — 4.42 — — Ethanol — — — 1.74 — — Silicone emulsion — 0.0025 0.00250.0025 — 0.0025 Sodium polyacrylate 1.4 — — — 1.4 — Polyethyleneimines —— 1.0 — — — NaOH Up to Up to Up to Up to Up to Up to pH 8 pH 8 pH 8 pH 8pH 8 pH 8 Na Formate — — — 0.02 — — Protease — — 0.45 0.29 — — Amylase —— 0.08 — — — Dye — 0.002 0.002 0.001 — 0.002 Perfume oil 0.5 2.0 0.6 1.51.2 0.8 Water Balance Balance Balance Balance Balance Balance ¹FirstGraft Copolymer: Graft copolymer described in Synthesis Example 1 withPVP/ PVAc-g-PEG at 20:30:50 by weight ratio with weight-average MW16,800 Dalton. ²Second Graft Copolymer: Polyvinyl acetate graftedpolyethylene oxide copolymer having a polyethyleneoxide backbone andmultiple polyvinyl acetate side chains, supplied by BASF, Germany

TABLE 3c Ingredients (weight %) M N O P Q R C₁₂-₁₄AE₁₋₃S 2.5 7.0 7.0 4.23.0 3.9 C₁₂-₁₄AS 1.0 5.3 5.3 1.2 — — C₁₁-₁₃LAS 10.7 9.7 9.7 5.4 4.2 3.9C₁₂-₁₄EO₇ 10.8 6.2 6.2 5.4 3.0 5.9 First Graft Copolymer¹ 0.3 1.0 0.51.2 0.4 0.9 Second Graft Copolymer² 0.2 0.3 0.5 0.4 0.2 0.3 C₁₂-C₁₈fatty acid — — 2.0 — 2.6 1.1 Na-DTPA 0.05 0.05 0.05 0.18 0.64 0.09 NaOHUp to Up to Up to Up to Up to Up to pH 8 pH 8 pH 8 pH 8 pH 8 pH 8Perfume oil 1.2 1.0 0.75 1.5 1.0 0.8 Additional ingredients BalanceBalance Balance Balance Balance Balance (including water) ¹First GraftCopolymer: Graft copolymer described in Synthesis Example 1 with PVP/PVAc-g-PEG at 20:30:50 by weight ratio with weight-average MW 16,800Dalton. ²Second Graft Copolymer: Polyvinyl acetate grafted polyethyleneoxide copolymer having a polyethyleneoxide backbone and multiplepolyvinyl acetate side chains, supplied by BASF, Germany

Example 3: Exemplary Formulations of Unite Dose Laundry DetergentCompositions

The exemplary formulations as shown in Table 4 are made for unit doselaundry detergent. These compositions are encapsulated intocompartment(s) of the unit dose by using a polyvinyl-alcohol-based film.

TABLE 4 Ingredients (weight %) S T U V W X Y C₁₁-C₁₃ LAS 8 6 5 1 8 6 5C₁₂-C₁₄AE₃S 6 10 5 2 6 10 5 C₁₄-C₁₅EO7 — 6 — — 9 10 11 C₁₂-C₁₄EO7 18 2516 18 9 15 5 First Graft 2 0.1 0.5 1.7 0.2 0.4 1.5 Copolymer¹ SecondGraft 1 0.2 1.5 0.7 1.0 2.0 1.5 Copolymer² Citric acid 0.5 0.7 1.1 0.50.5 0.7 1.1 C₁₂-C₁₈ fatty acid 0.5 2.4 0.5 4.8 0.5 2.4 0.5 Sodium cumene1.3 — 1.3 1.3 1.3 1.3 1.3 sulphonate Perfume oil 0.3 1.5 2.5 3.0 4.0 0.81.0 Solvent Balance Balance Balance Balance Balance Balance Balance1First Graft Copolymer: Graft copolymer described in Synthesis Example 1with PVP/ PVAc-g-PEG at 20:30:50 by weight ratio with weight-average MW16,800 Dalton. ²Second Graft Copolymer: Polyvinyl acetate graftedpolyethylene oxide copolymer having a polyethyleneoxide backbone andmultiple polyvinyl acetate side chains, supplied by BASF, Germany

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A laundry detergent composition, comprising: 1) afirst graft copolymer comprising: a) polyalkylene oxide as a graft basewhich has a number average molecular weight of from about 1000 to about20,000 Daltons and is based on ethylene oxide, propylene oxide, butyleneoxide, or a mixture thereof; b) N-vinylpyrrolidone as side chains; andc) vinyl ester component as side chains which is derived from asaturated monocarboxylic acid containing from 1 to 6 carbon atoms and/ora methyl or ethyl ester of acrylic or methacrylic acid; wherein theweight ratio of (a):(b) is from about 1:0.1 to about 1:2, and whereinthe amount, by weight, of (a) is greater than the amount of (c); 2) asecond graft copolymer comprising: i) polyalkylene oxide component as agraft base; and ii) vinyl ester component as side chains; and 3) aperfume.
 2. The laundry detergent composition according to claim 1,wherein the weight ratio of the first graft copolymer to the secondgraft copolymer is from about 20:1 to about 1:20.
 3. The laundrydetergent composition according to claim 1, wherein the weight ratio ofthe first graft copolymer to the second graft copolymer is about 5:1 toabout 1:5.
 4. The laundry detergent composition according to claim 1,wherein the weight ratio of the first graft copolymer to the secondgraft copolymer is from about 3:1 to about 1:3.
 5. The laundry detergentcomposition according to claim 1, wherein the total amount of the firstgraft copolymer and the second graft copolymer in the laundry detergentcomposition is from about 0.05% to about 3.0%, by weight of thecomposition.
 6. The laundry detergent composition according to claim 1,wherein the total amount of the first graft copolymer and the secondgraft copolymer in the laundry detergent composition is from about 0.2%to about 1%, by weight of the composition.
 7. The laundry detergentcomposition according to claim 1, wherein the weight ratio of the firstgraft copolymer to the second graft copolymer is from about 3:1 to about1:3, and the total amount of the first graft copolymer and the secondgraft copolymer in the laundry detergent composition is from about 0.2%to about 1%, by weight of the composition.
 8. The laundry detergentcomposition according to claim 1, wherein in the graft polymer a) thepolyalkylene oxide comprises ethylene oxide units or ethylene oxideunits and propylene oxide units, and b) the vinyl ester comprises vinylacetate.
 9. The laundry detergent composition according to claim 1,wherein in the graft polymer a) the polyalkylene oxide consists ofethylene oxide units or ethylene oxide units and propylene oxide units,and b) the vinyl ester consists of vinyl acetate.
 10. The laundrydetergent composition according to claim 1, wherein in the first graftcopolymer, the polyalkylene oxide has a number average molecular weightof from about 2000 to about 15,000 Daltons.
 11. The laundry detergentcomposition according to claim 1, wherein in the graft polymer, theweight ratio of (a):(c) is from about 1.0:0.1 to about 1.0:0.99.
 12. Thelaundry detergent composition of claim 1, wherein in the graft polymer,the weight ratio of (a):(c) is from about 1.0:0.3 to about 1.0:0.9. 13.The laundry detergent composition according to claim 1, wherein in thefirst graft copolymer, from about 30 mol % to about 50 mol % of thegrafted-on monomers of component (c) are hydrolysed.
 14. The laundrydetergent composition according to claim 1, wherein the first graftcopolymer has a weight average molecular weight of from about 8,000 Dato about 20,000 Da.
 15. The laundry detergent composition according toclaim 1, wherein said second graft copolymer has an average of greaterthan 0 to less than or equal to 1 graft site per 50 alkylene oxideunits, and/or wherein said second graft copolymer has from about 25% toabout 60%, by weight of said polymer of the polyalkylene oxide componentand from about 40% to about 75%, by weight of said polymer of the vinylester component, and/or wherein said second graft copolymer has a meanmolar mass Mw of from about 6,000 to about 45,000; and/or wherein saidsecond graft copolymer has a polydispersity of less than or equal to 3;and/or wherein said second graft copolymer comprises less than or equalto about 10% by weight of the polyvinyl ester in ungrafted form; and/orwherein said second graft copolymer comprises side chains consisting ofthe vinyl ester component.
 16. The laundry detergent compositionaccording to claim 1, wherein the composition comprises: from about 0.1%to about 1%, by weight of the composition, of the first graft copolymer,and/or from about 0.1% to about 1%, by weight of the composition, of thesecond graft copolymer, and/or from about 0.008% to about 2%, by weightof the composition, of the perfume.
 17. The laundry detergentcomposition according to claim 1, further comprises from 0.1% to 70%, byweight of the composition, of a surfactant.
 18. The laundry detergentcomposition according to claim 17, wherein the surfactant comprisesC₆-C₂₀ linear alkylbenzene sulfonate, C₆-C₂₀ alkyl alkoxy sulfates,C₆-C₂₀ alkoxylated alcohol, or any mixtures thereof.
 19. The laundrydetergent composition according to claim 1, wherein said composition isin the form of a liquid composition, a granular composition, asingle-compartment pouch, a multi-compartment pouch, a sheet, a pastilleor bead, a fibrous article, a tablet, a bar, flake, or a mixturethereof.
 20. A method of treating textile, the method comprising thesteps of: (i) treating a textile with a laundry detergent compositionaccording to claim 1; and (ii) treating the textile with a fabricenhancer composition comprising a perfume.